Self-assembly of long-chain quaternary ammonium cations in a hybrid inorganic–organic material with one-dimensional polymeric tribromido­plumbate(II)

catena-Poly[benzyl­decyl­dimethyl­ammonium [plumbate(II)-tri-μ-bromido]], {(C₁₉H₃₄N)[PbBr₃]}_n, crystallizes as an inorganic–organic hybrid following monoclinic space-group symmetry P2₁/c. The structure consists of extended chains running along the [001] direction and built of [PbBr₃]⁻ units. These inorganic chains are separated by inter­digitated ammonium cations which form hydro­philic layers through weak C—H...Br inter­actions. The architecture is essentialy the same as found for n-alkyl­benzyl­dimethyl­ammonium bromides.

S1. Comment

A persistent problem in solid-state inorganic chemistry is the correlation of structural features, characteristic for a particular type of materials, with their physical properties. In this connection, low-dimensional compounds play an important role, because the interactions between atoms and molecules, when confined to one or two dimensions, make theoretical models much simpler (Day, 1983). Many useful physical and chemical properties could only be found and defined in terms of low-dimensional structural models. For example, the architecture of alternate hydrophobic and hydrophilic layers, as observed in the crystals of alkylbenzylammonium bromides (Hodorowicz et al., 2005), provided an explanation of the structure of ammonium cation layers formed at the surface or intercalated between the silicate units, such as those observed in Na–montmorillonite (Kwolek et al., 2003). This knowledge could be utilized in the crystal engineering of organoclays for specific applications. On the other hand, halometalates(II) represent particularly suitable systems for designing the construction of low-dimensional structural archetypes from which modifications with enhanced properties could be derived. The synthesis of inorganic–organic hybrids based on n-alkylbenzyldimethylammonium cations and inorganic [{PbBr₃}^-]_n chains represents an attempt to combine the properties of organic and inorganic domains to modify the macroscopic properties of the crystalline phase (Mitzi et al., 2001; Portier et al., 2001). Some of the low-dimensional polymeric halometalates of copper(II), manganese(II) and cadmium(II) have been studied previously (Ravindran et al., 1990, and references therein; Bonamartini-Corradi et al., 1993, 1994). Also, tin derivatives have been exploited due to their nonmagnetic semiconducting properties (Willett, 1991). Concerning haloplumbates, much work has been carried out on iodoplumbates(II) of the AM_zX_2z+1 type due to their potential semiconducting properties (quantum-wire systems) (Papavassiliou, 1997). Among these systems containing MX₆ face-sharing octahedra, there are compounds like [Et₄NPbI₃]_n and [Bu₄NPbI₃]_n with short-chain quaternary ammonium cations (Papavassiliou, 1997). A few years ago, the structures of the inorganic–organic hybrids {Bu₂[PbI₃]I.2H₂O}_n (Billing & Lemmerer, 2006) and {[(CH₃)₂C═ NHCH₂CH₂CH₃][PbI₃]} (Elleuch et al., 2007) were reported. The composition and structure of iodoplumbate anions (chains, ribbons or rods) are determined by the size, shape and charge of the counter-ions used for crystallization (Krautscheid et al., 2001). Much less is known about bromoplumbate(II) systems with long-chain organic ammonium molecules. In the present paper, we report the investigation of the structure of the inorganic–organic hybrid complex salt, (I), containing one-dimensional polymeric bromoplumbate(II) anions built of face-sharing {PbBr₆) (distorted) octahedra and quaternary benzyldecyldimethylammonium cations. The aim of this work was to increase our knowledge of the factors controlling the stereochemistry of bromoplumbates(II) and the mutual packing properties of long-chain quaternary ammonium cations in different environments, particularly in relation to their behaviour in crystalline bromides (Hodorowicz et al., 2005).

The title compound belongs to a family of one-dimensional inorganic–organic hybrid solids with the general formula AMX₃, in which A is an organic ammonium cation, M is a divalent metal, in our case Pb^II, and X is Cl, Br, or I (Cheetham et al., 2006). The structure consists of the long hydrocarbon chain benzyldecyldimethylammonium cations and [{PbBr₃}^-]_n polymeric chains as counter-ions. The assymmetric part of the unit cell contains the ammonium cation and a [PbBr₃^- unit (Fig. 1). The displacement parameters of the atoms in the decyl chain clearly increase along the chain and the highest displacements were observed for the terminal C atoms, which have additional degrees of freedom. This and some unusually short C—C bonds in some parts of the chain (Table 1) are a consequence of complex unmodelled disorder in the chain. The curvature of hydrocarbon chain is not as severe as observed in analogous bromides (Hodorowicz et al., 2005). Each Pb^II atom is surrounded in a one-dimensional polymeric chain by six bridging Br atoms, three of which are crystallographically independent. The polymeric chain runs along the a axis. The Pb—Br bond lengths [2.942 (1)–3.050 (1) Å; Table 1], agree well with those observed for other haloplumbates(II), for example, [PbBr₃]^- and [PbI₃]^- (Nagapetyan et al., 1988). All the Pb—Br bond lengths are shorter than the sum of the ionic radii (Pb²⁺ = 1.20 Å and Br^- = 1.96 Å), probably due to partially covalent interactions. The Pb—Br bond lengths and Br—Pb—Br angles differ significantly from regular octahedral values. As a consequence, the {PbBr₆} unit has barely C₁ symmetry, with the triangular bromide faces (Br2, Br3 and Br4) shared by two adjacent polyhedra (Fig. 2). The nonbonding intramolecular Pb···Pb distances are 3.8437 (2) Å. The angle of Pb1ⁱ—Pb1—Pb1ⁱⁱ angle of 179.48 (1)° [symmetry codes: (i) x, -y+3/2, z-1/2; (ii) x, -y+3/2, z+1/2] indicates a linear development of the one-dimensional polymeric chains. Figs. 3 and 4 show the alternating hydrophilic and hydrophobic layers viewed along [100] and [001], respectively. In Fig. 3, the mode of mutual packing of the polymeric [{PbBr₃}^-]_n chains and the benzyldecyldimethylammonium cations is presented. The polymeric [{PbBr₃}^-]_n chains parallel to [100] and the >N⁺(CH₃)₂ moieties of the quaternary ammonium cations form hydrophilic layers through weak C—H···Br interactions (geometry given in Table 2). The hydrophobic layers are built of the benzyl and decyl groups of the ammonium cations, the mutual arrangement of which are defined by the three torsion angles N1—C4—C41—C46, C1—N1—C4—C41 and C11—C1—N1—C4 (Table 1), indicating synclinal/+synclinal/+synclinal conformations, respectively. The conformation of the decyl group is of zigzag type (all trans conformations). In the layers, the decyl chains are antiparallel to one another and are joined via weak C—H···π interactions belonging to category I of the Malone weak-hydrogen-bond classification (Malone et al., 1997). The C—H···π interactions (Fig. 5) are responsible for the self-assembly of ammonium cations in the hydrophobic layers (Table 2).

In conclusion, an organic–inorganic layered hybrid material based on benzyldecyldimethylammonium cations, which interact with adjacent [{PbBr₃}^-]_n inorganic chains, has been obtained and structurally characterized. Due to a hydrophobic effect, the architecture of the bilayers, built of interdigitated ammonium cations interacting via weak C—H···π bridges, is preserved in the crystalline state irrespective of the counter-ion type. These properties predispose the ammonium cations to be utilized in the crystal engineering of layered materials as structure-directing agents (Rey et al., 2004; Shen et al., 2003). On the other hand, the incorporation of organic ions into inorganic frameworks opens the way for the engineering of a new class of layered multifunctional materials.

Related literature

For related literature, see: Billing & Lemmerer (2006); Bonamartini-Corradi, Bruckner, Cramarossa, Manfredini, Menabue, Saladini, Sccani, Sandrolini & Giusti (1993); Bonamartini-Corradi, Cramarossa, Manfredini, Giusti, Battaglia, Saccani & Sandrolini (1994); Cheetham et al. (2006); Day (1983); Elleuch et al. (2007); Hodorowicz et al. (2005); Krautscheid et al. (2001); Kwolek et al. (2003); Malone et al. (1997); Mitzi et al. (2001); Nagapetyan et al. (1988); Papavassiliou (1997); Portier et al. (2001); Ravindran et al. (1990); Rey et al. (2004); Sheldrick (2008); Shen et al. (2003); Willett (1991).

S2. Experimental

All chemicals were of reagent grade quality obtained from commercial sources and used without further purification. The crystalline phase was obtained using a mixture of aqueous solutions of Pb(NO₃)₂ and the ammonium bromide in a 1:2 molar ratio. Well shaped crystals were obtained by slow evaporation at room temperature.

S3. Refinement

Suitable single crystals of the title compound were carefully selected using a polarizing microscope. The anisotropic atomic displacement parameters of all non-H atoms were restrained using rigid-bond and pseudo-isotropic restraints (DELU 0.01 0.01 and ISOR 0.1 0.2 instructions of SHELXL97; Sheldrick, 2008). This was deemed necessary because of the strong absorption of the material and the unmodelled disorder in the organic side chain. H atoms were included from geometrical constraints in a riding model assuming C—H = 0.97 Å for CH₂ groups, 0.96 Å for CH₃ groups and 0.93 Å for CH groups of benzene rings.

Computing details

Data collection: COLLECT (Nonius, 1997); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and BS (Ozawa & Kang, 2004); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. View of the asymmetric unit of (I), showing the atomic numbering scheme. Displacement ellipsoids are shown at the 30% probability level. The mutual arrangement of benzyl and long-chain substituents in the alkylbenzylammonium cation is defined by two torsion angles, viz. C41—C4—N1—C1 and C4—N1—C1—C11, indicating a synclinal conformation.
	Fig. 2. The geometry of the [PbBr3^-]n chain extended along [100]. [Symmetry codes: (i) x, -y+3/2, z-1/2; (ii) x, -y+3/2, z+1/2.]
	Fig. 3. The crystal packing, viewed along [100], showing the layered architecture of ammonium cations and polymeric [PbBr3]^- chains running along [100]. H atoms have been omitted for clarity.
	Fig. 4. Projection along [001] clearly emphasizing the organic–inorganic hybrid nature of the material.
	Fig. 5. Self-assembly of the ammonium cations in hydrophobic layers, with C13—H···Cg1 and C16—H···Cg1 interactions indicate by dotted line, where Cg1 is the centroid of the C41–C46 benzene ring.

catena-poly[benzyldecyldimethylammonium [plumbate(II)-tri-µ-bromido]]

Crystal data

(C19H34N)[PbBr3]	F(000) = 1368
Mr = 723.39	Dx = 1.910 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.4354 (1) Å	Cell parameters from 5124 reflections
b = 34.7040 (5) Å	θ = 1.0–28.7°
c = 7.6873 (1) Å	µ = 11.47 mm^−1
β = 92.062 (1)°	T = 293 K
V = 2515.55 (6) Å^3	Needle, colourless
Z = 4	0.19 × 0.06 × 0.05 mm

Data collection

Nonius KappaCCD diffractometer	6250 independent reflections
Radiation source: fine-focus sealed tube	3604 reflections with I > 2σ(I)
Horizontally mounted graphite crystal monochromator	Rint = 0.030
Detector resolution: 9 pixels mm^-1	θmax = 28.5°, θmin = 2.8°
ϕ and ο scans to fill Ewald sphere	h = −12→12
Absorption correction: multi-scan (DENZO and SCALEPACK; Otwinowski & Minor, 1997)	k = −46→32
Tmin = 0.219, Tmax = 0.598	l = −10→0
9624 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.039	H-atom parameters constrained
wR(F^2) = 0.076	w = 1/[σ^2(Fo^2) + (0.0106P)^2 + 3.275P] where P = (Fo^2 + 2Fc^2)/3
S = 1.01	(Δ/σ)max = 0.003
6250 reflections	Δρmax = 0.67 e Å^−3
221 parameters	Δρmin = −0.52 e Å^−3
194 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00081 (6)

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
N1	0.3711 (4)	0.82919 (14)	0.7120 (6)	0.0620 (12)
C1	0.2369 (5)	0.84799 (17)	0.6444 (7)	0.0634 (15)
H1A	0.2107	0.8678	0.7262	0.076*
H1B	0.1620	0.8288	0.6413	0.076*
C2	0.4148 (7)	0.7976 (2)	0.5922 (9)	0.097 (2)
H2A	0.4537	0.8086	0.4898	0.145*
H2B	0.3336	0.7822	0.5596	0.145*
H2C	0.4851	0.7817	0.6505	0.145*
C3	0.3404 (7)	0.8118 (2)	0.8855 (8)	0.088 (2)
H3A	0.3131	0.8318	0.9640	0.132*
H3B	0.4237	0.7991	0.9320	0.132*
H3C	0.2646	0.7935	0.8715	0.132*
C4	0.4947 (5)	0.8571 (2)	0.7350 (9)	0.0779 (18)
H4A	0.5796	0.8424	0.7644	0.093*
H4B	0.5091	0.8697	0.6243	0.093*
C11	0.2440 (6)	0.8660 (2)	0.4655 (8)	0.0800 (18)
H11A	0.3135	0.8866	0.4691	0.096*
H11B	0.2746	0.8467	0.3835	0.096*
C12	0.1025 (7)	0.8819 (2)	0.4041 (9)	0.093 (2)
H12A	0.0752	0.9023	0.4823	0.111*
H12B	0.0318	0.8617	0.4090	0.111*
C13	0.1037 (8)	0.8977 (3)	0.2203 (10)	0.121 (3)
H13A	0.1714	0.9187	0.2195	0.145*
H13B	0.1394	0.8776	0.1459	0.145*
C14	−0.0268 (9)	0.9114 (3)	0.1419 (11)	0.125 (3)
H14A	−0.0658	0.9303	0.2201	0.151*
H14B	−0.0925	0.8899	0.1356	0.151*
C15	−0.0240 (9)	0.9293 (3)	−0.0362 (11)	0.130 (3)
H15A	0.0428	0.9505	−0.0278	0.156*
H15B	0.0170	0.9103	−0.1120	0.156*
C16	−0.1439 (10)	0.9433 (3)	−0.1232 (14)	0.159 (4)
H16A	−0.1873	0.9612	−0.0443	0.191*
H16B	−0.2085	0.9216	−0.1361	0.191*
C17	−0.1441 (10)	0.9621 (3)	−0.2901 (12)	0.142 (4)
H17A	−0.0874	0.9852	−0.2735	0.171*
H17B	−0.0911	0.9454	−0.3652	0.171*
C18	−0.2660 (13)	0.9735 (4)	−0.3891 (16)	0.210 (6)
H18A	−0.3154	0.9500	−0.4227	0.252*
H18B	−0.3266	0.9869	−0.3097	0.252*
C19	−0.2620 (12)	0.9956 (4)	−0.5349 (14)	0.191 (5)
H19A	−0.3567	1.0031	−0.5703	0.287*
H19B	−0.2205	0.9811	−0.6265	0.287*
H19C	−0.2061	1.0182	−0.5108	0.287*
C41	0.4784 (6)	0.8874 (2)	0.8697 (9)	0.0746 (16)
C42	0.5422 (8)	0.8821 (2)	1.0338 (10)	0.098 (2)
H42	0.5899	0.8592	1.0591	0.118*
C43	0.5358 (11)	0.9102 (3)	1.1587 (13)	0.131 (3)
H43	0.5791	0.9061	1.2677	0.157*
C44	0.4673 (11)	0.9438 (4)	1.1258 (15)	0.141 (4)
H44	0.4625	0.9624	1.2124	0.169*
C45	0.4053 (9)	0.9503 (3)	0.9651 (14)	0.126 (3)
H45	0.3592	0.9735	0.9416	0.151*
C46	0.4113 (7)	0.9221 (2)	0.8365 (11)	0.095 (2)
H46	0.3696	0.9268	0.7271	0.114*
Pb1	0.87732 (2)	0.750252 (7)	0.98516 (2)	0.05543 (10)
Br2	0.66563 (6)	0.78536 (2)	1.22246 (8)	0.0746 (2)
Br3	1.10409 (6)	0.77713 (2)	1.23811 (7)	0.06660 (19)
Br4	0.86569 (6)	0.81763 (2)	0.75282 (8)	0.07328 (19)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.045 (2)	0.064 (3)	0.077 (3)	−0.002 (2)	0.007 (2)	−0.001 (2)
C1	0.049 (3)	0.067 (4)	0.074 (4)	−0.001 (3)	0.009 (3)	−0.007 (3)
C2	0.088 (5)	0.077 (5)	0.126 (6)	0.021 (4)	0.013 (4)	−0.025 (4)
C3	0.088 (5)	0.087 (6)	0.087 (4)	−0.018 (4)	−0.004 (4)	0.020 (4)
C4	0.041 (3)	0.091 (5)	0.103 (5)	−0.008 (3)	0.010 (3)	−0.002 (4)
C11	0.079 (4)	0.086 (5)	0.075 (4)	−0.006 (4)	−0.003 (3)	0.001 (3)
C12	0.094 (5)	0.081 (6)	0.102 (5)	0.012 (4)	−0.008 (4)	0.006 (4)
C13	0.115 (6)	0.120 (8)	0.125 (6)	−0.016 (5)	−0.029 (5)	0.042 (5)
C14	0.121 (6)	0.132 (8)	0.122 (6)	0.013 (6)	−0.010 (5)	0.021 (6)
C15	0.119 (7)	0.138 (9)	0.132 (7)	0.009 (6)	−0.021 (5)	0.034 (6)
C16	0.133 (7)	0.168 (11)	0.176 (9)	0.039 (7)	0.002 (6)	0.060 (8)
C17	0.158 (8)	0.140 (9)	0.128 (7)	0.025 (7)	−0.007 (6)	0.031 (6)
C18	0.176 (10)	0.246 (16)	0.208 (13)	0.052 (11)	−0.003 (9)	0.101 (11)
C19	0.213 (12)	0.196 (14)	0.163 (10)	0.010 (10)	−0.024 (9)	0.056 (8)
C41	0.060 (4)	0.069 (4)	0.094 (4)	−0.016 (3)	0.002 (3)	0.006 (3)
C42	0.095 (5)	0.097 (6)	0.102 (5)	−0.029 (4)	−0.013 (4)	0.016 (4)
C43	0.135 (8)	0.153 (9)	0.105 (6)	−0.051 (7)	−0.006 (6)	−0.010 (6)
C44	0.137 (9)	0.134 (8)	0.152 (8)	−0.044 (7)	0.023 (7)	−0.053 (8)
C45	0.117 (7)	0.075 (6)	0.186 (9)	−0.016 (5)	0.016 (6)	−0.017 (6)
C46	0.085 (5)	0.071 (5)	0.128 (6)	−0.013 (4)	−0.006 (4)	0.007 (4)
Pb1	0.05189 (14)	0.07954 (18)	0.03502 (12)	−0.00273 (11)	0.00378 (8)	−0.00064 (11)
Br2	0.0637 (4)	0.1004 (5)	0.0600 (4)	0.0208 (3)	0.0060 (3)	0.0061 (4)
Br3	0.0586 (3)	0.0865 (5)	0.0546 (3)	−0.0130 (3)	0.0007 (3)	−0.0009 (3)
Br4	0.0624 (4)	0.0738 (5)	0.0846 (4)	0.0005 (3)	0.0154 (3)	0.0032 (4)

Geometric parameters (Å, º)

N1—C2	1.499 (7)	C16—H16A	0.9700
N1—C1	1.501 (6)	C16—H16B	0.9700
N1—C3	1.502 (7)	C17—C18	1.412 (11)
N1—C4	1.522 (7)	C17—H17A	0.9700
C1—C11	1.514 (8)	C17—H17B	0.9700
C1—H1A	0.9700	C18—C19	1.360 (12)
C1—H1B	0.9700	C18—H18A	0.9700
C2—H2A	0.9600	C18—H18B	0.9700
C2—H2B	0.9600	C19—H19A	0.9600
C2—H2C	0.9600	C19—H19B	0.9600
C3—H3A	0.9600	C19—H19C	0.9600
C3—H3B	0.9600	C41—C46	1.381 (9)
C3—H3C	0.9600	C41—C42	1.390 (9)
C4—C41	1.487 (9)	C42—C43	1.371 (12)
C4—H4A	0.9700	C42—H42	0.9300
C4—H4B	0.9700	C43—C44	1.352 (13)
C11—C12	1.505 (8)	C43—H43	0.9300
C11—H11A	0.9700	C44—C45	1.367 (12)
C11—H11B	0.9700	C44—H44	0.9300
C12—C13	1.516 (9)	C45—C46	1.393 (11)
C12—H12A	0.9700	C45—H45	0.9300
C12—H12B	0.9700	C46—H46	0.9300
C13—C14	1.432 (9)	Pb1—Br4	2.9420 (7)
C13—H13A	0.9700	Pb1—Br3	2.9883 (6)
C13—H13B	0.9700	Pb1—Br2	3.0106 (6)
C14—C15	1.505 (10)	Pb1—Br2^i	3.0504 (6)
C14—H14A	0.9700	Pb1—Br3^i	3.0627 (6)
C14—H14B	0.9700	Pb1—Br4^ii	3.1323 (7)
C15—C16	1.381 (10)	Br2—Pb1^ii	3.0504 (6)
C15—H15A	0.9700	Br3—Pb1^ii	3.0627 (6)
C15—H15B	0.9700	Br4—Pb1^i	3.1323 (7)
C16—C17	1.440 (11)
C2—N1—C1	110.7 (4)	C15—C16—C17	124.5 (9)
C2—N1—C3	108.6 (5)	C15—C16—H16A	106.2
C1—N1—C3	107.1 (4)	C17—C16—H16A	106.2
C2—N1—C4	108.1 (4)	C15—C16—H16B	106.2
C1—N1—C4	113.4 (5)	C17—C16—H16B	106.2
C3—N1—C4	108.9 (5)	H16A—C16—H16B	106.4
N1—C1—C11	115.4 (4)	C18—C17—C16	125.6 (10)
N1—C1—H1A	108.4	C18—C17—H17A	105.9
C11—C1—H1A	108.4	C16—C17—H17A	105.9
N1—C1—H1B	108.4	C18—C17—H17B	105.9
C11—C1—H1B	108.4	C16—C17—H17B	105.9
H1A—C1—H1B	107.5	H17A—C17—H17B	106.2
N1—C2—H2A	109.5	C19—C18—C17	123.8 (12)
N1—C2—H2B	109.5	C19—C18—H18A	106.4
H2A—C2—H2B	109.5	C17—C18—H18A	106.4
N1—C2—H2C	109.5	C19—C18—H18B	106.4
H2A—C2—H2C	109.5	C17—C18—H18B	106.4
H2B—C2—H2C	109.5	H18A—C18—H18B	106.5
N1—C3—H3A	109.5	C18—C19—H19A	109.5
N1—C3—H3B	109.5	C18—C19—H19B	109.5
H3A—C3—H3B	109.5	H19A—C19—H19B	109.5
N1—C3—H3C	109.5	C18—C19—H19C	109.5
H3A—C3—H3C	109.5	H19A—C19—H19C	109.5
H3B—C3—H3C	109.5	H19B—C19—H19C	109.5
C41—C4—N1	115.7 (5)	C46—C41—C42	117.6 (8)
C41—C4—H4A	108.4	C46—C41—C4	123.1 (7)
N1—C4—H4A	108.4	C42—C41—C4	119.1 (7)
C41—C4—H4B	108.4	C43—C42—C41	120.9 (9)
N1—C4—H4B	108.4	C43—C42—H42	119.6
H4A—C4—H4B	107.4	C41—C42—H42	119.6
C12—C11—C1	111.6 (5)	C44—C43—C42	121.0 (11)
C12—C11—H11A	109.3	C44—C43—H43	119.5
C1—C11—H11A	109.3	C42—C43—H43	119.5
C12—C11—H11B	109.3	C43—C44—C45	119.9 (11)
C1—C11—H11B	109.3	C43—C44—H44	120.1
H11A—C11—H11B	108.0	C45—C44—H44	120.1
C11—C12—C13	112.9 (6)	C44—C45—C46	119.9 (10)
C11—C12—H12A	109.0	C44—C45—H45	120.1
C13—C12—H12A	109.0	C46—C45—H45	120.1
C11—C12—H12B	109.0	C41—C46—C45	120.8 (8)
C13—C12—H12B	109.0	C41—C46—H46	119.6
H12A—C12—H12B	107.8	C45—C46—H46	119.6
C14—C13—C12	118.5 (7)	Br4—Pb1—Br3	99.039 (19)
C14—C13—H13A	107.7	Br4—Pb1—Br2	92.014 (19)
C12—C13—H13A	107.7	Br3—Pb1—Br2	87.391 (17)
C14—C13—H13B	107.7	Br4—Pb1—Br2^i	84.885 (19)
C12—C13—H13B	107.7	Br3—Pb1—Br2^i	173.57 (2)
H13A—C13—H13B	107.1	Br2—Pb1—Br2^i	97.60 (2)
C13—C14—C15	118.5 (8)	Br4—Pb1—Br3^i	83.211 (18)
C13—C14—H14A	107.7	Br3—Pb1—Br3^i	90.030 (18)
C15—C14—H14A	107.7	Br2—Pb1—Br3^i	174.16 (2)
C13—C14—H14B	107.7	Br2^i—Pb1—Br3^i	85.365 (17)
C15—C14—H14B	107.7	Br4—Pb1—Br4^ii	174.33 (2)
H14A—C14—H14B	107.1	Br3—Pb1—Br4^ii	81.286 (18)
C16—C15—C14	123.0 (9)	Br2—Pb1—Br4^ii	82.336 (18)
C16—C15—H15A	106.6	Br2^i—Pb1—Br4^ii	95.316 (19)
C14—C15—H15A	106.6	Br3^i—Pb1—Br4^ii	102.460 (18)
C16—C15—H15B	106.6	Pb1—Br2—Pb1^ii	78.714 (14)
C14—C15—H15B	106.6	Pb1—Br3—Pb1^ii	78.860 (14)
H15A—C15—H15B	106.5	Pb1—Br4—Pb1^i	78.443 (17)
C2—N1—C1—C11	−59.4 (7)	C43—C44—C45—C46	0.8 (16)
C3—N1—C1—C11	−177.6 (5)	C42—C41—C46—C45	−1.5 (10)
C4—N1—C1—C11	62.3 (7)	C4—C41—C46—C45	−176.7 (7)
C2—N1—C4—C41	−171.6 (6)	C44—C45—C46—C41	0.5 (13)
C1—N1—C4—C41	65.3 (7)	Br4—Pb1—Br2—Pb1^ii	−139.032 (18)
C3—N1—C4—C41	−53.8 (7)	Br3—Pb1—Br2—Pb1^ii	−40.071 (17)
N1—C1—C11—C12	176.4 (5)	Br2^i—Pb1—Br2—Pb1^ii	135.86 (2)
C1—C11—C12—C13	−176.1 (6)	Br3^i—Pb1—Br2—Pb1^ii	−103.96 (15)
C11—C12—C13—C14	176.0 (8)	Br4^ii—Pb1—Br2—Pb1^ii	41.482 (17)
C12—C13—C14—C15	176.3 (8)	Br4—Pb1—Br3—Pb1^ii	131.479 (17)
C13—C14—C15—C16	179.7 (10)	Br2—Pb1—Br3—Pb1^ii	39.853 (18)
C14—C15—C16—C17	177.1 (10)	Br2^i—Pb1—Br3—Pb1^ii	−101.23 (15)
C15—C16—C17—C18	173.9 (12)	Br3^i—Pb1—Br3—Pb1^ii	−145.39 (2)
C16—C17—C18—C19	171.1 (13)	Br4^ii—Pb1—Br3—Pb1^ii	−42.789 (16)
N1—C4—C41—C46	−86.4 (8)	Br3—Pb1—Br4—Pb1^i	132.408 (14)
N1—C4—C41—C42	98.4 (7)	Br2—Pb1—Br4—Pb1^i	−139.914 (15)
C46—C41—C42—C43	1.3 (11)	Br2^i—Pb1—Br4—Pb1^i	−42.463 (16)
C4—C41—C42—C43	176.7 (7)	Br3^i—Pb1—Br4—Pb1^i	43.463 (15)
C41—C42—C43—C44	0.0 (14)	Br4^ii—Pb1—Br4—Pb1^i	−134.8 (2)
C42—C43—C44—C45	−1.0 (17)

Symmetry codes: (i) x, −y+3/2, z−1/2; (ii) x, −y+3/2, z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11B···Br3^iii	0.97	3.09	3.761 (7)	128
C3—H3C···Br3^iv	0.96	3.04	3.950 (7)	159
C2—H2B···Br3^iii	0.96	3.23	3.992 (7)	137
C4—H4A···Br4	0.97	2.84	3.757 (6)	159
C1—H1B···Br4^v	0.97	2.98	3.779 (5)	141
C42—H42···Br2	0.93	2.93	3.823 (8)	161
C2—H2C···Br2^i	0.96	2.93	3.837 (7)	159
C2—H2A···Br2^vi	0.96	3.03	3.788 (7)	137
C3—H3B···Br2	0.96	3.17	4.049 (6)	153
C13—H13A···Cg1^vi	0.97	3.37	3.989	123
C16—H16B···Cg1^iii	0.97	3.22	3.880	127

Symmetry codes: (i) x, −y+3/2, z−1/2; (iii) x−1, y, z−1; (iv) x−1, −y+3/2, z−1/2; (v) x−1, y, z; (vi) x, y, z−1.